Functional member, and method for production thereof and fluid to be applied

ABSTRACT

There is provided a functional member, which is excellent in terms of a humidity controlling function, a removal function of toxic chemicals and an unpleasant living odor, antifouling properties, stain concealing properties, and flexibility. A functional member is provided with a first layer which is formed on a flexible base material and comprises a dry matter of a mixture comprising an inorganic porous material and an organic emulsion, and a second layer comprising an inorganic filler which is fixed over an approximately entire surface of the first layer by an organic binder, wherein the organic matter in the organic emulsion has a glass-transition temperature of −5° C. to −50° C.; and the organic binder in the second layer is contained in an amount of 30-300 parts by volume to 100 parts by volume of the inorganic filler.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a functional member, which is excellentin terms of a humidity controlling function to autonomously control arelative humidity in a space, a removal function of toxic chemicals andan unpleasant living odor, antifouling properties, stain concealingproperties, flexibility and the like, and a method and an coating liquidfor producing the functional member.

2. Background Art

There has been known a humidity control building material with moistureabsorbing/releasing performance. The humidity control building materialis a building material to autonomously control a relative humidity in aspace, which can absorb moisture in high humidity and release moisturein low humidity. Since, in living environments of recent years, moisturetends to accumulate in a room by virtue of improved heat insulation andairtight properties, a necessity of a humidity control building materialis being heightened.

On the other hand, in recent years there is a problem that an indoorenvironmental pollution by toxic chemicals causes health disturbancesuch as sick house syndrome. Also, a demand for deodorizing anunpleasant living odor such as a toilet odor, a garbage odor, or a petodor is still strong. And thus, it is still desirable that the humiditycontrol building material has not only moisture absorbing/releasingperformance but also a capability of adsorbing and removing toxicchemicals or an unpleasant odor in indoor air. Moreover, it is obviousthat a surface of such a humidity control material is desirablystain-resistant.

Japanese Patent Laid-Open Publication No. 2000-117916 discloses adecorative material comprising a moisture absorbing/releasing resinlayer and a permeable film of polyethylene or the like laminated on asurface of the moisture absorbing/releasing resin layer, thereby toimpart contamination resistance thereto. Further, Japanese PatentLaid-Open Publication No. 2001-1479 discloses a decorative materialcomprising a moisture absorbing/releasing resin layer and a surfaceprotective layer comprising a moisture permeable urethane resin formedon a surface of the moisture absorbing/releasing resin layer, thereby toimpart contamination resistance thereto.

Japanese Patent Laid-Open Publication No. 01-113236 discloses a ceramicplate comprising a humidity controlling layer and a decorative layerwith communicating air holes formed on the humidity controlling layer,thus improving design performance. Furthermore, Japanese PatentLaid-Open Publication No. 2000-43221 discloses a decorative materialcomprising a moisture absorbing/releasing resin layer and a decoratedpermeable sheet laminated on the moisture absorbing/releasing resinlayer, thus improving design performance.

SUMMARY OF THE INVENTION

The inventors of the present invention have now found that forming, on aflexible base material, a first layer comprising a dry matter of amixture comprising an inorganic porous material and a particular organicemulsion, and further forming a second layer comprising an inorganicfiller and an organic binder at a certain ratio over an approximatelyentire surface of the first layer can provide a functional member whichis excellent in a humidity controlling function, a removal function oftoxic chemicals and an unpleasant living odor, antifouling properties,stain concealing properties, and flexibility.

Therefore, an object of the present invention is to provide a functionalmember excellent in a humidity controlling function, a removal functionof toxic chemicals and an unpleasant living odor, antifoulingproperties, stain concealing properties and flexibility, and a methodand an coating liquid for producing the functional member.

A functional member according to the present invention comprises:

a flexible base material,

a first layer which is formed on the base material and comprises a drymatter of a mixture comprising an inorganic porous material and anorganic emulsion, and

a second layer comprising an inorganic filler which is fixed over anapproximately entire surface of the first layer by an organic binder,

wherein the organic emulsion has a glass-transition temperature of −5°C. to −50° C., and

wherein the organic binder in the second layer is contained in an amountof 30-300 parts by volume to 100 parts by volume of the inorganicfiller.

Further, a method of producing a functional member according to thepresent invention comprises the steps of:

providing a flexible base material,

applying an coating liquid comprising an inorganic porous material andan organic emulsion in which a glass-transition temperature of anorganic matter is −5° C. to −50° C. on the base material,

drying the coating liquid to form a first layer, and

applying a mixture of an inorganic filler and an organic binder over anapproximately entire surface of the first layer to form a second layer,wherein

the organic binder in the second layer is contained in an amount of30-300 parts by volume to 100 parts by volume of the inorganic filler.

Furthermore, a coating liquid to form a first layer of a functionalmember according to the present invention comprises an inorganic porousmaterial and an organic emulsion, wherein the organic matter of theorganic emulsion has a glass-transition temperature of −5° C. to −50° C.

DETAILED DESCRIPTION OF THE INVENTION

Functional Member

FIG. 1 shows an example of a functional member according to the presentinvention. A functional member according to the present inventioncomprises a base material 1, a first layer 2 and a second layer 3. Onthe base material 1 having flexibility, the first layer 2 is formedcomprising a dry matter of a mixture comprising an inorganic porousmaterial and an organic emulsion. The organic matter of the organicemulsion used in the first layer 2 has a glass-transition temperature of−5° C. to −50° C. As a result, the first layer 2 exhibits not onlymoisture absorbing/releasing performance of water vapor but alsoabsorption/removal performance of an indoor toxic chemical gas and anunpleasant living odor, as well as further has adequate flexibility.

Over an approximately entire surface of the first layer 2, the secondlayer 3 is formed. The second layer 3 comprises an inorganic filler andan organic binder fixing the inorganic filler. The organic binder iscontained in the second layer 3 in an amount of 30-300 parts by volumerelative to 100 parts by volume of the inorganic filler. According tothe second layer 3, while the moisture absorbing/releasing performanceto water vapor and the adsorption/removal performance to a stain by thefirst layer 2 are adequately secured, antifouling properties and stainconcealing properties to a stain such as cigarette tar can be achieved.That is, the second layer 3 prevents a stain from being transmitted tosome extent without blocking water vapor transmission, thus exhibitingantifouling properties. However, so as to achieve the above functions ofthe first layer 2 to the full, the second layer 3 does not completelyprevent a stain from being transmitted but rather allows it to betransmitted therethrough to some extent. And, even when a stain such ascigarette tar is transmitted through the second layer 3 to be adsorbedin the first layer 2, a stain thereof is concealed by the inorganicfiller which is contained in the second layer 3 by a predeterminedamount, thereby preventing the stain from standing out. In other words,stain concealing properties can be obtained. As described above,according to the functional material of the present invention, themoisture absorbing/releasing performance and the contaminant removalperformance can be compatible with the antifouling properties and stainconcealing properties at a lower price. Furthermore, while thefunctional member of the present invention is a multilayer structurewith such multi-functions, the functional member has flexibility. Forthis reason, the functional member of the present invention can be usedfor a wide range of applications including a building interior material,a vehicle interior material and the like.

Base Material

The base material used in the present invention is a base materialhaving flexibility, preferably, the base material having properties ofnot being broken even when folded at an angle of 180°. Preferredexamples of the base material include a paper, a synthetic resin sheet,a woven fabric, a non-woven fabric, a glass fiber sheet, a metal fiber,a flame-retardant backing paper, a base material paper for wall papers,a composite or a laminated material thereof, or other base materialswhich can be generally used for wall papers of vinyl cloth or the like.

When the functional member of the present invention is used as abuilding wall paper, a base material paper for wall papers is preferablyused in terms of cost and productivity. More preferably, a base materialpaper having a three-layer structure comprising a backing paper, a film,and a non-woven fabric is used. On the non-woven fabric of the basematerial paper, a first layer is formed, and thus, adhesion of the firstlayer is improved by a so-called anchoring effect. Further, the film isdisposed between the non-woven fabric and the backing paper. Therefore,when an coating liquid is applied to the base material, a wrinkle can beprevented from being generated on the base material paper. As thebacking paper, so as to exhibit normal workability as a wall paper, awater-absorbing paper is preferable. It is preferable that the film isformed of a synthetic resin such as polyethylene, and is a non-permeablelaminate film which acts as a water resistant layer. Disposing a layerof the non-permeable laminate film between the backing paper and thenon-woven fabric prevents moisture from being moved from the paper tothe first layer in construction, which therefore, can achieveworkability comparable to that of normal vinyl cloth. Such a basematerial paper is mostly a combustible material made mainly of organicmatters, and therefore, it is preferable that in terms of fireresistance, the base material paper weight is equal to or less than 150g/m².

First Layer

A first layer in the present invention comprises a dry matter of amixture comprising an inorganic porous material and an organic emulsion.Since the first layer is porous due to the inorganic porous material andhas a larger surface area, the first layer has excellent moistureabsorbing/releasing performance to water vapor and excellentadsorption/removal performance to toxic chemicals or an unpleasantliving odor. The inorganic porous material in the present invention maybe any one with a fine pore which can absorb/release moisture byadsorbing/desorbing water vapor. Preferred examples of the inorganicporous material include alumina-silica xerogel porous material, silicagel, activated alumina, mesoporous zeolite, mesoporous silica, porousglass, apatite, diatomaceous earth, sepiolite, allophane, imogolite,activated clay or the like.

According to a preferred embodiment of the present invention, it ispreferable that a volume of a fine pore of which a diameter is 4-14nmmeasured by nitrogen gas adsorption of the inorganic porous material isequal to or more than 0.1 ml/g and that a total volume of all the finepores of which each diameter is 1-200 nm measured by nitrogen gasadsorption of the inorganic porous material is equal to or less than 1.5ml/g. Owing to the above, excellent antifouling properties to a tarstain and the moisture absorbing/releasing performance can be obtained.In particular, humidity thereof can be efficiently adjusted autonomouslywithin a range of a relative humidity between 40% and 70%, which isregarded to be the most comfortable.

A fine pore diameter and a fine pore volume of the inorganic porousmaterial can be measured by the Barrett Joyner Halenda method with theuse of a desorption isotherm obtained from a result of measurement of anadsorption/a desorption isotherm by nitrogen gas adsorption. A specificsurface area/fine pore distribution analyzer used in the method iscommercially available, and with the use of such a commerciallyavailable analyzer, the fine pore diameter and the fine pore volume ofthe inorganic porous material can be measured.

According to a preferred embodiment of the present invention, a volumeaverage particle size of the inorganic porous material is preferably20-60 μm. The particle size can be measured with a laserdiffraction/scattering particle size analyzer. Hereby, a crack is notgenerated, there are very few uneven portions on the surface, and theimproved appearance can be obtained.

The inorganic porous material in the present invention can be obtainedas a commercially available material but also can be produced asfollows.

An example of methods of producing an alumina-silica xerogel porousmaterial will be described in the following. First of all, aluminumnitrate nonahydrate and tetraethyl orthosilicate are dissolved inethanol at a predetermined ratio of SiO₂ to Al₂O₃. At the time, whenneeded, a predetermined amount of water is added to adjust a solution.The solution is stirred for 3 hours, and thereafter, 25% ammonia wateris added therein, and the solution is coprecipitated to gelate. Agelling substance thus obtained is rapidly dried and thereafter fired at300° C. for 4 hours to obtain an alumina-silica xerogel porous material.

As an example of methods of manufacturing activated alumina, a method ofselectively dissolving kaolin mineral is listed. In this method, thekaolin mineral is calcined at 900° C. to 1200° C. to cause a phaseseparation of amorphous silica and a spinel layer. It is preferable thata calcination temperature is, though depending on impurities of thekaolin mineral or the like, 950° C. to 1050° C. in general and further,the kaolin mineral is heated for approximately 1 to 24 hours. Phaseseparation substances obtained by heat treatment as described above aretreated with alkali or hydrofluoric acid, and thereby, amorphous silicais selectively dissolved and the dissolved portion is formed as a finepore.

In this case, as alkali treatment of the phase separation substances,KOH aqueous solution of approximately 1-5 mol/l is preferably used.Moreover, by maintaining a heating condition of approximately 50° C. to150° C. for approximately 1-100 hours in the alkali treatment, amorphoussilica is completely dissolved and a fine pore having a sufficientvolume can be formed.

As another example of methods of manufacturing activated alumina, a pHswing synthetic method is listed. In the method, acid salt of aluminumand an aqueous solution of basic salt are mixed to depositpseudoboehmite gel. Specifically, the mixing is preferably performed byalternately adding acid salt of aluminum and basic salt to adjust the pHto be equal to 2 and 10. A preferred example of the acid salt isaluminum nitrate, and a preferred example of the basic salt is sodiumaluminate. The pseudoboehmite gel thus produced has particles grown byrepeating pH swings, and by controlling the number of each of the swingsand the swing pH, a deposited particle size of the pseudoboehmite gelcan be controlled. The pseudoboehmite gel of which a particle size iscontrolled, obtained in this way, is heated/fired, whereby thepseudoboehmite is γ-aluminized to obtain activated alumina with finepores formed thereon from the particle pore space. That is, bycontrolling a deposited particle size of the pseudoboehmite gel, a finepore size of the activated alumina after heating/firing can becontrolled.

As organic emulsion in the present invention, there is used organicemulsion in which an organic matter such as a resin having aglass-transition temperature between −5° C. and −50° C. is dispersedinto a dispersion medium such as water or alcohol. This allows animprovement of flexibility of the functional material. A preferableglass-transition temperature in the organic matter is equal to or lessthan −30° C. Preferred examples of the organic emulsion include acrylicemulsion, acrylic styrene emulsion, acrylic silicone emulsion, ethylenevinyl acetate emulsion, silicone emulsion, vinyl acetate acrylicemulsion, vinyl acetate emulsion, vinyl acetate veova emulsion, urethaneacrylic composite emulsion, silica modified acrylic copolymer emulsion,styrene acrylic urethane composite emulsion, ethylene vinyl acetateacrylic composite emulsion, vinyl acetate malate copolymer aqueousemulsion, ethylene-vinyl ester copolymer aqueous emulsion, fluorineemulsion or the like.

According to a preferred embodiment of the present invention, it ispreferable that 200-500 parts by weight of the inorganic porous materialis compounded relative to 100 parts by weight of a dry matter of theorganic emulsion. And in this way, excellent moistureabsorbing/releasing performance and flexibility can be obtained.

According to another preferred embodiment of the present invention, itis preferable that a formulation ratio in a mixture to form a firstlayer is 400-1200 parts by volume of the inorganic porous material to100 parts by volume of an emulsion dry matter of the organic matter.Hereby, excellent moisture absorbing/releasing performance can beobtained and also, a sense of tackiness hardly remains on the surfaceafter being dried and further, flexibility is improved. Therefore, afunctional member which can autonomously adjust relative humidity in aspace such as a living environment or the like to approximately 40-70%that makes people feel comfortable and further has flexibility can beproduced with the improved appearance.

Further, according to a more preferred embodiment of the presentinvention, it is preferable that a volume of a fine pore of which adiameter is 4-14 nm measured by nitrogen gas adsorption of the inorganicporous material is equal to or more than 0.2 ml/g and that a totalvolume of all the fine pores each diameter of which is 1-200 nm is equalto or less than 1.3 ml/g. Hereby, an adequate performance toautonomously adjust relative humidity in a space that makes people feelcomfortable can be obtained and also moisture in organic emulsion isless likely to fill fine pores, which therefore, improves coatability.Furthermore, in a case where a moisture adjustment is performed so as toobtain preferable viscosity as an coating liquid, a large amount ofmoisture is not needed, by which the first layer can be efficientlydried and the productivity is improved. Furthermore, a crack can beprevented from being generated on the first layer in drying. A range ofa fine pore volume is preferably equal to or less than 1.0 mg/l.

According to a further preferred embodiment of the present invention, itis preferable that the first layer further includes a non-porous filler.In the present invention, the non-porous filler means a filler of whicha total pore volume is less than 0.05 ml/g. A shape of the non-porousfiller may be any one of a spherical shape, a polyhedron, a flaky shape,a needle shape and the like. The non-porous filler does not absorbwater, and therefore, a moisture adjustment of an coating liquid is madeeasier and also a crack is prevented from being generated on the firstlayer in drying a coating film. Preferred examples of the non-porousfiller include silica, alumina, titania, zirconia, calcium carbonate,calcium hydroxide, aluminum hydroxide, talc, mica, wollastonite or thelike.

In an embodiment in use of the non-porous filler described above, it ismore preferable that a formulation ratio in a mixture to form a firstlayer is 400-1100 parts by volume of the inorganic porous material and50-500 parts by volume of the non-porous filler to 100 parts by volumeof an emulsion dry matter of an organic matter, and a total amount ofthe inorganic porous material and the non-porous filler is 400-1200parts by volume. Because of the above, a large amount of moisture is notneeded in a moisture adjustment of the coating liquid, by which thefirst layer can be efficiently dried and the productivity is improved.Still further, a crack can be prevented from being generated on thefirst layer in drying.

Moreover, in an embodiment in use of the non-porous filler describedabove, it is preferable that a volume of a fine pore of which a diameteris 4-14 nm measured by nitrogen gas adsorption of the inorganic porousmaterial is equal to or more than 0.4 ml/g and that a total volume ofall the fine pores each diameter of which is 1-200 nm measured bynitrogen gas adsorption of the inorganic porous material is equal to orless than 1.6 ml/g. Owing to the above, excellent moistureabsorbing/releasing performance can be obtained and also a sense oftackiness hardly remains on a surface thereof after being dried, andfurthermore, the flexibility is improved. Therefore, a functional memberwhich can autonomously adjust relative humidity in a space such as aliving environment to be approximately 40-70% that makes people feelcomfortable and also has the flexibility can be produced with theimproved appearance.

According to a preferred embodiment of the present invention, a volumeaverage particle size of the non-porous filler is 5-60 μm. Because ofthe above, a crack is not generated, there are very few uneven portionson the surface, and the improved appearance can be obtained.

According to a preferred embodiment of the present invention, it ispreferable that a particle diameter of an organic matter in the organicemulsion to form a first layer is smaller than a particle size of theinorganic porous material and also a number average particle sizethereof is equal to or more than 0.2 μm. This prevents an organic matterin the emulsion from being excessively dense, adequately securing apermeation pathway to the inorganic porous material, and moistureabsorbing/releasing properties can be fully exhibited. A preferableparticle diameter of the organic emulsion is equal to or less than 1 μm.

According to a preferred embodiment of the present invention, it ispreferable that the inorganic porous material is an approximatelyspherical particle. With the use of an approximately spherical particlehaving an improved fluidity, a filling ratio of the inorganic porousmaterial in the coat is increased, which therefore, can improve moistureabsorbing/releasing performance.

According to a preferred embodiment of the present invention, a coatthickness of the first layer is preferably 50-500 μm. Hereby, adequatemoisture absorbing/releasing properties can be exhibited and also weightper unit area thereof is appropriate, and flexibility thereof issuitable for construction. Furthermore, when the coat thickness is inthe range described above, a coating method by a comma coater can beused as in the case of a production of normal vinyl cloth. Therefore,productivity thereof is improved.

According to a preferred embodiment of the present invention, 0.1-5parts by weight of a germicide or a fungicide is compounded in 100 partsby weight of a mixture before being dried to form a first layer. Hereby,excellent antibacterial properties or antifungal properties can beimparted to a functional member. Especially, the functional member ofthe present invention has excellent moisture absorbing/releasingproperties and therefore, is inevitably in a state of constantlycontaining water vapor, whereby bacteria or molds tend to be generatedthereon. For this reason, it can be said that compounding a germicide ora fungicide to the first layer of the functional member is particularlyeffective. Also, a germicide and a fungicide may be used together or anagent effective to both bacteria and molds may be used.

The germicide and the fungicide in the present invention may be eitheran organic or inorganic one.

Examples of the organic germicide and fungicide include a germicide anda fungicide such as a type of triazole, alcohol, phenol, aldehyde,carboxylic acid, ester, ether, nitrile, peroxide epoxy, halogen,pyridine quinoline, triazine, isothiazolone, imidazole thiazole,anilide, biguanide, disulfide, thiocarbamate, surfactant or organicmetal.

Examples of the inorganic germicide and the fungicide include agermicide and a fungicide such as a type of ozone, chlorine compound,iodine compound, peroxide, boric acid, sulfur, calcium, sodiumsilicofluoride silico fluoroto sodium or metal ion.

According to a preferred embodiment of the present invention, as thegermicide or the fungicide, a metal ion type is preferably used. Suchantibacterial metal ions are retained and fixed in a solid more easilycompared to hypochlorous acid, ozone or the like. Further, a neededamount of ions can be extracted therefrom by controlling an ion elutionrate, and accordingly, the metal ions are suitable for longer-term use.Preferred examples of the antibacterial metal ion include silver ion,copper ion, zinc ion or the like.

Examples of the substance to release the antibacterial metal ion includea compound including a dissoluble antibacterial metal element such assilver lactate, silver nitrate, silver acetate, silver sulfate, cuprousacetate, cupric acetate, copper nitrate, cuprous sulfate, cupricsulfate, zinc acetate, zinc nitrate, zinc chloride, or zinc sulfate. Inparticular, since a silver ion has a beneficial effect on bacteria, andalso a copper ion has a beneficial effect on fungi, it is preferablethat one of the ions is selected properly or both of the ions are usedtogether. Further, in order to control a release rate of anantibacterial component or the like, an antibacterial component such asan ion of silver, copper, or zinc, a compound thereof, or single metalcolloid may be carried in a pore or a crystal lattice of a carrier ofinorganic oxide or the like. Carriers therefor include apatite, calciumphosphate, zirconium phosphate, aluminum phosphate, titania, layeredsilicate, layered aluminosilicate, zeolite or the like. Furthermore,chlorine resistance may be secured by silver thiosulfate complex whichis obtained by anionizing silver ion highly-reactive to chlorine.

Other examples of the germicide or the fungicide include a naturalproduct-derived agent or a fungicide that is obtained from animals orplants. Specific examples thereof include chitin/chitosan,aminoglycoside compound, hinokitiol, mugwort extract, aloe extract,perilla leaf extract, Houttunia cordata, licorice, theaceous plantextract, natural sulfur, mustard/Japanese horseradish extract, bambooextract or the like. In addition, a photocatalyst may also be used.Examples thereof include anatase titanium dioxide, rutile titaniumdioxide, tungsten trioxide, bismuth trioxide, iron trioxide, strontiumtitanate, tin oxide, zinc oxide or the like. They may be of a sphericalshape or a scale shape, fibrous powder, or in a sol state.

According to a preferred embodiment of the present invention, it ispreferable that a germicide or fungicide added to the first layer issoluble in water. Hereby, it is possible to provide at a lower cost afunctional member that has a humidity controlling performance and thatachieves adequate antibacterial properties or antifungal properties overall the layers of a multilayered structure thereof even if the firstlayer has a higher moisture content. That is, a water-soluble germicideor fungicide is added to the first layer, and thereby, even when thefirst layer absorbs water vapor to have the higher moisture content, thewater-soluble germicide or fungicide is diffused into the entire firstlayer through the medium of adsorbed water. As a result, adequateantibacterial properties or antifungal properties can be achieved in thefirst layer. And also, the water-soluble germicide or fungicide isdiffused into other layers in addition to the first layer. Consequently,though the germicide or the fungicide is added only to the first layer,adequate antibacterial properties or antifungal properties can beachieved in all the layers of the functional member. It is preferablethat the water-soluble fungicide is mainly organic. Specific examplesthereof include a water-soluble fungicide such as a type of triazole,alcohol, phenol, aldehyde, carboxylic acid, ester, ether, nitrile,peroxide epoxy, halogen, pyridine quinoline, triazine, isothiazolone,imidazole thiazole, anilide, biguanide, disulfide, thiocarbamate,surfactant, organic metal or the like.

Second Layer

A second layer according to the present invention is a layer comprisingan inorganic filler and an organic binder fixing the inorganic fillerover an approximately entire surface of the first layer. The secondlayer can prevent a contaminant such as cigarette tar from beingtransmitted therethrough to some extent without blocking water vaportransmission. Further, even when the contaminant such as cigarette taris transmitted through the second layer to be adsorbed in the firstlayer, it is possible to make a stain adhering to the first layer lessvisible since the contaminant is concealed by a predetermined amount ofthe inorganic filler containing in the second layer. And therefore,antifouling properties and appearance thereof are improved.

The second layer is formed over the approximately entire surface of thefirst layer, thus improving antifouling properties and appearance overthe approximately entire surface of the functional member. In thepresent invention, the approximately entire surface means that 90% ormore of the first layer is covered.

The second layer in the present invention contains the organic binder inan amount of 30-300 parts by volume to 100 parts by volume of theinorganic filler. In the range, adequate adhesion to a lower layer canbe obtained and also concealing properties to conceal a stain adheringto the first layer are improved, thereby making it possible to improvethe appearance. In addition, there is an advantage in cost.

According to a preferred embodiment of the present invention, a coatthickness of the second layer is preferably 1-100 μm. In the range,adequate antifouling properties can be obtained and also, obstruction tothe water vapor transmission is reduced and there is a little influenceon a moisture absorbing/releasing amount. Additionally, there is anadvantage in cost.

According to a preferred embodiment of the present invention, a particlediameter of the inorganic filler is preferably equal to or less than 60μm. In the range, a space between the particles becomes smaller, thusimproving an antifouling effect and making a surface thereof becomesmooth in appearance.

According to a preferred embodiment of the present invention, it ispreferable that the inorganic filler contains either titanium oxide orcalcium carbonate. Each of the substances is a white material excellentin concealing properties and efficiently conceals a tar stain adsorbedin the first layer. Further, by forming the second layer with a whitematerial such as titanium oxide or calcium carbonate or the like, a gooddesign is advantageously imparted on the second layer. Furthermore,color pigment is added to the second layer so that the second layer canfunction as a designed layer. Still further, a designed layer may beformed on a surface of the second layer on which a good design isimparted as described above.

In a preferred embodiment of the present invention, the organic binderis a cured product of the organic emulsion. In this way, it is possibleto form a second layer in an industrially lower-cost method. Herein, theorganic emulsion means a substance in which organic components arestably dispersed into water.

In a preferred embodiment of the present invention, a glass-transitiontemperature of the organic matter in the organic emulsion to form asecond layer is set to be −10° C. to 30° C. When the glass-transitiontemperature is equal to or more than −10° C., in actual use conditions,in other words, in the vicinity of room temperature, a sense oftackiness is not generated and tar is less likely to adhered to thesecond layer. Moreover, when the glass-transition temperature is equalto or less than 30° C., the second layer has flexibility, and as aresult, the second layer is hardly cracked and even when a flexible basematerial is folded, there is no fold mark left.

Preferred examples of the inorganic filler used in the second layeraccording to the present invention include titanium oxide, calciumcarbonate, aluminum hydroxide, silica, alumina, zirconia or the like andbesides, a natural raw material such as silica sand or porcelain stonecrushed material. Examples of the color pigment include metal oxide suchas titanium yellow, spinel green, zinc flower, colcothar, chrome oxide,cobalt blue, or iron black; metal hydroxide such as alumina white oryellow iron oxide; ferrocyanide compound such as Prussian blue; leadchromate such as chrome yellow, zinchromate, or molybdenum red; sulfidesuch as zinc sulfide, vermilion, cadmium yellow, or cadmium red;selenium compound; sulfate such as barite or precipitated bariumsulfate; carbonate such as heavy calcium carbonate or precipitatedcalcium carbonate; silicate such as hydrous silicate, clay, orultramarine blue; carbon such as carbon black; metal powder such asaluminum powder, bronze powder, or zinc powder; pearl pigment such asmica/titanium oxide; phthalocyanine; azo pigment or the like.

Examples of the organic binder used in the second layer according to thepresent invention include organic emulsion, water-soluble resin,photocurable resin or the like. From a viewpoint of forming a secondlayer in the industrially lower-cost method, the organic emulsion isparticularly preferable.

Preferred examples of the organic emulsion used in forming a secondlayer include emulsion such as acryl, acrylic styrene, acrylic silicone,ethylene vinyl acetate, silicone, acrylic vinyl acetate, vinyl acetate,vinyl acetate veova, urethane acryl, styrene acryl urethane composite,ethylene vinyl acetate acrylic composite, vinyl acetate malatecopolymer, ethylene-vinyl ester-based copolymer, fluorine, orfluoroacrylate.

In a preferred embodiment of the present invention, the second layerand/or the water repellent layer further comprises at least one of thegermicide and the fungicide, thus achieving further antibacterialperformance or antifungal performance. The germicide or the fungicideused in the second layer and/or the water repellent layer may be thesame as the germicide or the fungicide used in the first layer.

In a preferred embodiment of the present invention, it is preferablethat the second layer further comprises a water-repellent additive. Withthis, it is possible to easily obtain a functional member havingantifouling properties to a tar stain and a moisture absorbing/releasingperformance and furthermore antifouling properties to a liquid stain. Apreferable content of the water-repellent additive in the second layeris 0.1-100 parts by weight to 100 parts by weight of the inorganicfiller.

Preferred examples of the water-repellent additive include a siliconetype or fluorine resin type. Specific examples of the silicone typewater-repellent additive include a silicon compound which has siloxanechain [—Si(R¹, R²)—O—Si(R¹, R²)—O-(in the formula, each of R¹ and R²independently represents a hydrogen atom or alkyl group.)], or silanechain [—Si(R³, R⁴)—Si(R³, R⁴)-(in the formula, each of R³ and R⁴independently represents a hydrogen atom or alkyl group.)] in a moleculeof polysiloxane, polymethylsiloxane, polydimethylsiloxane or the like,or silicone resin or the like.

Specific examples of the fluorine resin type water-repellent additiveinclude organic resin including a fluorine atom in a raw materialmonomer, more specifically, fluorine resin such as polyethylenetetrafluoride, tetrafluorinated-perfluoro-alkoxyethylene copolymer (PFAresin), polyethylene chloride trifluoride, polyvinylidene fluoride,polyvinyl fluoride or fluoric rubber, or a fluorine-containingsurfactant. In the above additives, in terms of water-repellentperformance, the fluorine resin additive is preferably used.

Designed Layer

According to a preferred embodiment of the present invention, it ispreferable that a designed layer is further formed on the surface of thesecond layer. In the present invention, the designed layer is a layerhaving a pattern or a design, being embossed, or the like, a material ofwhich is not limited. The designed layer can be formed by the samemethod as gravure printing, screen printing or the like used inmanufacture of normal vinyl cloth.

According to a preferred embodiment of the present invention, it ispreferable that the designed layer is formed by foam printing. In thisway, a good design is imparted and at the same time, an effect as acontamination control layer of the first layer can be attained as is thecase with the second layer. As foam printing paint, printing paint forwall papers that has been conventionally used can be used without anylimitation in particular, and specifically, an example thereof includesa paint in which resin and a blowing agent are mixed.

Preferred examples of the resin component include acrylic resin, acrylicstyrene resin, acrylic silicone resin, ethylene vinyl acetate resin,silicone resin, vinyl acetate acrylic resin, vinyl acetate resin, vinylacetate veova resin, urethane acrylic composite resin, silica modifiedacrylic copolymer resin, styrene acrylic urethane composite resin,ethylene vinyl acetate acrylic composite resin, vinyl acetate malatecopolymer aqueous resin, ethylene-vinyl ester-based copolymer aqueousresin, fluorine resin or the like.

As the blowing agent, a conventionally-used decomposition gas-generatingblowing agent or an expandable capsule blowing agent or the like can beused. Preferred examples of the decomposition gas-generating blowingagent include azodicarbonamide, dinitroso penta-methylene tetramine,paratoluenesulfonyl hydrazide, benzenesulfonyl hydrazide, sodiumbicarbonate, ammonium carbonate or the like. Examples of the expandablecapsule blowing agent indlude an agent that contains a hydrocarbon-typevolatile expansion component such as ethane, butane, pentane,neopentane, hexane, or heptane in a minute particle containingthermoplastic resin such as acrylic ester, vinylidene chloride,acrylonitrile, or urethane as a coat.

According to a preferred embodiment of the present invention, areacoverage of a foam printing layer to the first layer is preferably equalto or more than 60%. And thereby, an effect as the contamination controllayer is adequately attained.

According to a preferred embodiment of the present invention, it ispreferable that a deodorant is compounded to the foam printing layer.Thereby, a removal function to toxic chemicals, an unpleasant livingodor and the like obtained by the first layer can be further improved.Examples of the deodorants include a porous substance to deodorize byphysical adsorption, an oxidation-reduction substance and a catalystsubstance to deodorize an odor substance by chemical reaction. Examplesof the porous substance to deodorize by physical adsorption include,besides the inorganic porous material described above, activated carbon,attached activated carbon, bentonite, silica-magnesia and the like.Examples of the oxidation-reduction substance and the catalyst substanceinclude a metal compound such as sulfate, nitrate, acetate, citrate,organic acid salt, oxide, hydroxide, phthalocyanine complex or otherchelate containing a metal selected from manganese, copper, zinc,cobalt, magnesium, iron, nickel, and zinc; a platinum group metalcompound; an inorganic substance of a type of iron-manganese, titanium,silica-alumina, metal oxide photocatalyst or the like; organic amines;an artificial enzyme; a clathrate compound such as cyclodextrin or crownether; and plant extract such as phytoncide, flavonoid, tannin,catechin, and essential oil.

According to a more preferred embodiment of the present invention, it ispreferable that a cover layer of a dry matter of a resin colloidaldispersion is further formed on the designed layer surface. Thereby, itis possible to form a contamination control layer without damagingmoisture absorbing/releasing properties. A preferred particle size ofthe resin colloidal dispersion is 1-100 nm, more preferably 5-100 nm.When the particle size is equal to or more than 5 nm, the moistureabsorbing/releasing properties are hardly damaged, and when the particlesize is equal to or less than 100 nm, a stain such as cigarette tar isless likely to be transmitted, thus providing an effect as thecontamination control layer. Preferred examples of the resin colloidaldispersion include a colloidal dispersion such as acryl, acrylicstyrene, acrylic silicone, ethylene vinyl acetate, silicone, acrylicvinyl acetate, vinyl acetate, vinyl acetate veova, urethane acryl,styrene acrylic urethane composite, ethylene vinyl acetate acryliccomposite, vinyl acetate malate copolymer, ethylene-vinyl ester-basedcopolymer, fluorine, fluoroacrylate.

Water Repellent Layer

According to a preferred embodiment of the present invention, it ispreferable that a water repellent layer is further formed on the secondlayer surface or the designed layer surface. In the present invention,the water repellent layer is a layer of which a surface comes in contactwith water at an angle equal to or more than 90 degrees. Thereby, it ispossible to form a surface which prevents water from being transmittedtherethrough without deteriorating water vapor transmission. Therefore,antifouling properties to a liquid stain of coffee or the like areimproved. The water repellent layer can be formed, for instance, byapplying water-repellent resin of a type of olefin, silicone orfluorine, or a water-repellent agent such as wax.

According to a preferred embodiment of the present invention, it ispreferable that the designed layer is formed on the second layer surfaceand further on the surface of the designed layer, a water repellentlayer is formed. Also, according to a more preferred embodiment of thepresent invention, the water-repellent treatment layer is preferablyformed on a foam printing layer. Thereby, by a synergistic effect ofuneven portions of the foam printing layer and water-repellentproperties by water-repellent treatment, that is, so-called a fractaleffect, particularly excellent water-repellent properties are achieved,and antifouling properties to a liquid stain are more prominentlyachieved.

Photocatalyst

According to a preferred embodiment of the present invention, it ispreferable that an outermost layer of the functional material furthercomprises a photocatalyst. Such outermost layers can be the secondlayer, the designed layer and the water-repellent layer. Moreover,according to another preferred embodiment of the present invention, thephotocatalyst may be fixed to the outermost layer of the functionalmaterial. Thereby, a function of decomposing adsorbed toxic chemicalscan also be imparted.

Examples of the photocatalyst include titanium oxide, zinc oxide,strontium titanate, tin oxide, vanadium oxide or tungsten oxide.Titanium oxide is more preferable in terms of stability of the materialitself, a photocatalyst activity, availability and the like, andespecially preferably, anatase titanium oxide. According to a morepreferred embodiment of the present invention, it is preferable that ametal to impart antibacterial/antifungal performance or improve aphotocatalyst activity is carried on the photocatalyst. Examples of sucha metal include gold, silver, copper, zinc, platinum or the like.

It is preferable that an amount of adding a photocatalyst particle tothe water repellent layer is 1-40 parts by weight to 100 parts by weightof a solid content of the water repellent layer.

Application

An application of the functional member according to the presentinvention is not particularly limited, and an extremely wide range ofapplications are considered. Preferred applications include a buildinginterior material for walls, floors, ceilings or the like, and a vehicleinterior material for automobiles, trains, ships, aircraft or the like,more preferably, a building wall paper.

When the functional member of the present invention is used as abuilding wall paper, it is preferable that in order to secure fireresistance, a dry weight of the organic emulsion for the first layer isequal to or less than 100 g/m², a dry weight of the organic emulsion forthe second layer is equal to or less than 50 g/m², and a total organicweight including the base material is equal to or less than 300 g/m².

Method and Coating Liquid for Producing Functional Member

In a method of producing a functional material of the present invention,as an coating liquid to form a first layer, a mixture comprising aninorganic porous material and an organic emulsion is provided. Theorganic emulsion comprises an organic matter having a glass-transitiontemperature of −5° C. to −50° C. The coating liquid may further comprisea non-porous filler.

After that, the coating liquid is applied on a flexible base material tobe dried for forming a first layer. The application of the coatingliquid on the base material can be performed, for instance, by dipping,spin coating, spraying, printing, flow coating, roll coating, acombination thereof or the like. A coat thickness of the first layer canbe controlled by changing a lifting speed in dipping, changing asubstrate rotating speed in spin coating, changing a solid contentconcentration or viscosity of the coating liquid, or the like.

When the coating liquid to form a first layer is mechanically applied bya comma coater or the like, it is preferable that an amount of watercontained in the coating liquid is 20-80 parts by weight to 100 parts byweight of a solid content thereof and the viscosity is 2000-8000 mPa·s.Hereby, the first layer can be coated on the base material surfacesuitably.

Drying and curing an coating liquid to form a first layer may beperformed by either drying at room temperature or forcible heating. Theforcible heating can be performed by heating and drying with farinfrared radiation, drying by hot air heating, or the like. In thiscase, the drying temperature is preferably equal to or more than 100° C.in terms of productivity.

Further, a mixture of an inorganic filler and an organic binder isapplied over an approximately entire surface of the first layer to forma second layer. The mixture is adjusted so that the organic binder iscontained in an amount of 30-300 parts by volume to 100 parts by volumeof the inorganic filler.

Application of the mixture to form a second layer can be performed byknown application methods, but is preferably performed by a gravureprinting method, a screen printing method or a combination thereof. Inthis case, a coat thickness thereof can be adjusted by controlling asolid content concentration or viscosity of the coating liquidcontaining the inorganic filler or by controlling a printing speed. Itshould be noted that, in order to form a second layer as a thin layer,use of the gravure printing method is preferable.

Preferred dilute solutions for adjusting the solid content concentrationor viscosity of the coating liquid to form a second layer include wateror alcohol such as isopropylalcohol or ethanol. Industrially, thealcohol dilute solution is preferably used, whereby a drying temperatureafter coating can be lower and the drying time can also be shorter.

Drying and curing of the coating liquid to form a second layer may beperformed by either drying at room temperature or forcible heating. Theforcible heating can be performed by heating and drying with farinfrared radiation, drying by hot air heating or the like. In this case,the heating temperature is preferably equal to or more than 100° C. interms of productivity.

According to a preferred embodiment of the present invention, it ispreferable that the coating liquid to form a designed layer or a waterrepellent layer is further applied on the second layer surface to bedried. The designed layer or the water repellent layer can be formed byknown application methods, but is preferably formed by a gravureprinting method, a screen printing method, or a combination thereof.Drying and curing of the water repellent layer may be performed byeither drying at room temperature or forcible heating, but is preferablyperformed by forcible heating in terms of productivity. The forcibleheating can be performed by heating/drying with far infrared radiation,drying by hot air heating or the like. At the time, the heatingtemperature is preferably equal to or higher than 100° C. in terms ofproductivity.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a view showing an example of a layered structure of afunctional material according to the present invention and correspondsto a sample produced in Example Al. The functional material comprises abase material 1, a first layer 2 formed on the base material 1 andfurther a second layer 3 formed on the first layer 2.

FIG. 2 is a graph showing an evaluation result of moistureabsorbing/releasing performance of each of samples produced in ExamplesA1 to A3 and A7 and Comparative Examples A1 and A3 to A5.

FIG. 3 is a view showing a layered structure of a functional materialproduced in Example A2. The functional material comprises a basematerial 1, a first layer 2 and second layer 3 formed on the basematerial 1, and further a water repellent layer 4 formed on the secondlayer 3.

FIG. 4 is a view showing a layered structure of a functional materialproduced in Example A3. The functional material comprises a basematerial 1, a first layer 2 and second layer 3 formed on the basematerial 1, and furthermore a designed layer 5 and water repellent layer4 formed on the second layer 3.

FIG. 5 is a view showing a layered structure of a functional materialproduced in Example A4. The functional material comprises a basematerial 1, a first layer 2 and second layer 3 formed on the basematerial 1, and a germicide 6 added into the second layer 3.

FIG. 6 is a view showing a layered structure of a functional materialproduced in Example A5. The functional material comprises a basematerial 1, a first layer 2 and second layer 3 formed on the basematerial 1, and a fungicide 7 added into the second layer 3.

FIG. 7 is a view showing a layered structure of a functional materialproduced in Example A6. The functional material comprises a basematerial 1, a first layer 2 and second layer 3 formed on the basematerial 1, furthermore a water repellent layer 4 formed on the secondlayer 3, and a photocatalyst 8 added into the water repellent layer 4.

FIG. 8 is a view showing a layered structure of a functional materialproduced in Example A7. The functional material comprises a basematerial 1, a first layer 2 and second layer 3 formed on the basematerial 1, and a water-repellent additive 9 added into the second layer3.

FIG. 9 is a view showing a layered structure of a functional materialproduced in Example A8. The functional material comprises a basematerial 1, a first layer 2 formed on the base material 1, andfurthermore a colored second layer 10 formed on the first layer 2.

FIG. 10 is a view showing a layered structure of a functional materialproduced in Example A9. The functional material comprises a basematerial 1, a first layer 2 and colored second layer 10 formed on thebase material 1, and furthermore a designed layer 5 and water repellentlayer 4 formed on the colored second layer 10.

FIG. 11 is a view showing a layered structure of a material produced ina Comparative Example A1. The material comprises a base material 1 and afirst layer 2 formed on the base material 1.

FIG. 12 is a view showing a layered structure of a material produced inComparative Example A2. The material comprises a base material 1, afirst layer 2 formed on the base material 1, and furthermore a waterrepellent layer 4 formed on the first layer 2.

FIG. 13 is a view showing a layered structure of a material produced inComparative Example A3. The material comprises a base material 1, afirst layer 2 formed on the base material 1, and furthermore a laminatefilm 11 formed on the first layer 2.

FIG. 14 is a view showing a layered structure of a material produced inComparative Example A4. The material comprises a base material 1, afirst layer 2 formed on the base material 1, and furthermore urethaneresin 12 formed on the first layer 2.

EXAMPLES

The present invention will be explained in more detail with reference tothe following examples, but is not limited to these examples.

Measuring methods of properties in raw materials with respect to thefollowing examples and comparative examples are as follows.

Measurement 1: Measurement of a Fine Pore Diameter and a Fine PoreVolume of an Inorganic Porous Material

With respect to a sample of approximately 0.2 g, the measurement of apore diameter and a pore volume thereof was made using a specificsurface area/pore distribution measurement device (ASAP 2000, made byMicromeritics, Inc.). This measuring device measuresadsorption/desorption isotherms of a nitrogen gas in each sample andmeasures fine pore diameters and volumes using the desorption isotherm.In addition, prior to the measurement, an inside of the device is heatedand degassed to less than 10⁻³ Torr at a temperature of 110° C., therebyremoving adsorbed components such as water vapors.

Measurement 2: Measurement of an Average Particle Size of an InorganicPorous Material and an Inorganic Filler

The measurement of a volume average particle size was made using a laserdiffraction/scattering particle distribution measuring device (Lasermicronsizer LMS-30 made by SEISHIN ENTERPRISE CO., LTD.).

Measurement 3: Measurement of Bulkiness Density of an Inorganic PorousMaterial, a Non-porous Filler, and an Inorganic Particulate

The measurement of bulkiness density was made using a tap densitymeasuring device (Tap denser-KYT-4000 made by SEISHIN ENTERPRISE CO.,LTD.).

Measurement 4: Measurement of an Average Particle Size of OrganicEmulsion

The measurement of a number average particle size was made using a laserdiffraction/scattering particle distribution measuring device (Lasermicronsizer LMS-30 made by SEISHIN ENTERPRISE CO., LTD.).

Measurement 5: Measurement of an Average Particle Size of ResinColloidal Dispersion

The measurement of a number average particle size was made using Microtrap UPA 150 of NIKKISO Co., Ltd. by a dynamic light scattering method.

Measurement 6: Calculation of Glass-transition Temperature of OrganicEmulsion and Resin Colloidal Dispersion

In the case where organic matters dispersed in the organic emulsion usedin the Examples or resin dispersed in the resin colloidal dispersionused in the Examples were copolymers, a glass-transition temperature Tgof the organic matter and the resin was calculated using aglass-transition temperature of a homo polymer according to thefollowing formula.$\frac{1}{Tg} = {\sum\limits_{i = 1}^{n}\quad\left( {{Wi}\text{/}{Tgi}} \right)}$

(in the formula, Tg: Tg (K) of copolymer, Tgi: Tg (K) of homo polymer ofcopolymerization monomer, Wi: weight percentage of copolymerizationmonomer)

It should be noted that Tg of a homo polymer of a copolymerizationmonomer, namely Tgi, was used based upon the standard of Japan EmulsionIndustry.

Measurement 7: Measurement of Bulkiness Density of a Dry Matter ofOrganic Emulsion

Organic emulsion dispersion liquid was dried and bulkiness density ofthe dry matter was measured by an Archimedes method. In this case,kerosene was used as a solvent to measure it in such a manner as not tore-dissolve the dry matter.

An evaluation test method of a functional material sample produced inthe following examples and comparative examples is as follows.

Test 1: Adhesion Promotion Test of Cigarette Tar

A box of 3600 cm³ was prepared, only a bottom part of which was opened.A sample (5×5 cm) was attached to a side face of the box. Cigarettesmoke was put in through the bottom part of the box where the tar wasadhered for 30 minutes. A contamination state before and after taradhesion was measured using a color difference meter (ND-300A made byNIPPON DENSHOKU CO., LTD.). Five pieces of Mild Seven made by JT (tar 12mg/piece, nicotine 0.9 mg/piece) were used as cigarette.

Test 2: Measuring Method of Moisture Absorbing and ReleasingCharacteristics

First, the measuring sample was forced to equilibrium in a vessel at aconstant temperature of 23° C. and at constant humidity of 33% R.H.Next, the sample was put in a vessel at a constant temperature of 23° C.and at constant humidity of 93% R. H. to measure a moisture absorbingamount for 24 hours. And the sample was put again in a vessel at aconstant temperature of 23° C. and at constant humidity of 33% R.H. tomeasure a moisture releasing amount.

Test 3: Contamination Resistant Properties Evaluation Test

A staining matter was dropped on a sample surface (surface on which asecond layer was formed) and 24 hours later, a wiping test was made byJK wiper (150-s made by CRECIA Corp.). The evaluation standard is asfollows.

Coffee, soy sauce, and aqueous blue ink were used as staining matters.

A: Stain traces disappeared by wiping with water.

B: Stain did not disappear by wiping with water, but after the samplesurface was properly wiped with synthetic detergent concentratesolution, the sample surface was further wiped with water, and thesample surface was wiped without water, so that the stain tracesdisappeared.

C: After the sample surface was properly wiped with synthetic detergentconcentrate solution, it was further wiped with water, and then, even ifit was wiped without water, the stain traces still remained on thesample surface.

Test 4: Evaluation of Antibacterial Properties

An antibacterial evaluation was made according to a film adhesion methoddefined in JIS Z 2801 (2000 year). With respect to strains to be used,staphylococcus aureus was used as gram positive bacteria and colibacteria was used as gram negative bacteria according to JIS Z 2801(2000 year). Evaluation methods of results all were made based upon JISZ 2801, and samples having antibacteria active value of 2.0 or more wereevaluated as having antibacteria properties.

Test 5: Evaluation of Antifungal Properties

The test was made based upon a nutrition addition wet method amongantifungal test methods stipulated by Japan Health Housing Association.Aspergillus niger was used as strains. Evaluation methods of results allwere made based upon the antifungal test method stipulated by JapanHealth Housing Association. Concretely, the evaluation standard is asfollows.

5: no growth of fungal threads, even under the 40 time microscope

4: growth of fungal threads is not visible to the naked eye, but growthof fungal threads is slightly found out under the 40 time microscope.

3: growth of fungal threads is visible to the naked eye off and on, andgrowth of fungal threads is remarkably found out under the 40 timemicroscope.

2: colony generation of fungus on ½ of the entire surface of one side ofthe sample is clearly visible to the naked eye.

1: growth of fungus is clearly visible to the naked eye, and the growthof fungus spreads over the entire surface of one side of the sample.

Test 6: Evaluation of Flexibility

The sample was folded by 180 degrees and appearance of the foldedportion was evaluated visually. The evaluation standard is as follows.

A: no crack

B: partial crack

C: crack over the entire surface

Test 7: Evaluation of Firesafety

Concalory meter test stipulated under Building Standard Law was made.The evaluation result was made based upon Building Standard Law to labelsamples having 8 MJ/m² or less as passing the test.

Test 8: Appearance Evaluation of Produced Coat State

The produced coat state of the first layer was evaluated visually. Theevaluation standard is as follows.

A: good

B: slightly bad

C: defective

Test 9: Measuring Method of Contacting Angle

A contacting angle at the time when distilled water of 10 μ1 was droppedon a sample surface was measured by a contacting angle measuring device(CA-X type made by Kyowa InterFace Science Co., Ltd.).

EXAMPLE A1

As a base material, a base material paper for wall papers having threelayered structure composed of a backing paper, a film, and a non-wovenfabric was prepared. The weight of the base material paper for wallpapers was 111 g/m². Activated alumina was prepared as an inorganicporous material. Measurements 1 and 2 were made with respect to theactivated alumina. As a result, the volume of the fine pore having adiameter of 4 to 14 nm was 0.41 ml/g, the total fine pore volume was0.50 ml/g, and the average particle diameter was 30 μm. Acrylic emulsionwas prepared as organic emulsion. The measurements 4 and 6 were madewith respect to the emulsion. As a result, the glass transitiontemperature was −43° C., and the average particle size was 0.25 μm, andthe active substance were 60%.

Raw materials were put into the mixer based upon the formulation shownin Table 1 and mixed therein to obtain coating liquid. This coatingliquid was applied on the base material using a comma coater in such amanner that the thickness of the first layer after drying became 350 μmand dried the coating liquid at 150° C. to form the first layer. Theweight of the organic matter after drying was 80 g/m². TABLE 1Formulation of a Mixture Comprising an Inorganic Porous Material andOrganic Emulsion Formulation Part by Weight Activated alumina 70 Acrylicemulsion 30 Dispersing agent 17.5 [Flowlen TG - 750 W made by KyoeisyaChemical Co., Ltd.] Wetting agent 0.5 [Flowlen D - 90 made by KyoeisyaChemical Co., Ltd.] Defoamer 0.5 [Aqualen 8020 made by Kyoeisya ChemicalCo., Ltd.] Water 40

The coating liquid was prepared based upon the formulation in Table 2.This coating liquid was applied on the first layer by a screen printingso that the thickness of the second layer after drying became 10 μm.Subsequently, a sample was dried at 150° C. to obtain the sample havinga layered structure shown in FIG. 1. The weight of the organic matterafter drying was 10 g/m². Titanium oxide and calcium carbonate were usedas an inorganic filler. An average particle diameter of the titaniumoxide was 5 μm and an average particle diameter of the calcium carbonatewas 3 μm. Organic emulsion of ethylene-vinyl acetate was used as anorganic binder. A glass-transition temperature of an organic matter ofthe organic emulsion was 0° C. TABLE 2 Formulation Part by WeightTitanium oxide 10 Calcium carbonate 20 Organic emulsion 25 Dispersingagent 3 [Flowlen TG - 750 W made by Kyoeisya Chemical Co., Ltd.] Wettingagent 0.4 [Flowlen D - 90 made by Kyoeisya Chemical Co., Ltd.] Defoamer0.2 [Aqualen 8020 made by Kyoeisya Chemical Co., Ltd.] Water 10

EXAMPLE A2

The coating liquid was prepared based upon the formulation in Table 3.There was used a water repellent additive made by distilling fluoroacrylate water repellent additive Ode KCRDO varnish [active substance 15wt %] made by Intec Corp. with an Ode KS solvent made by Intec Corp.comprising isopropyl alcohol and water. This coating liquid was appliedon the second layer of the sample produced in Example A1 by gravureprinting so that the thickness of the second layer after drying became0.2 μm. Subsequently, a sample was dried at 150° C. to obtain the samplewhere a water repellent layer was further formed as shown in FIG. 3.TABLE 3 Formulation Part by weight Fluoro acrylate water repellentadditive 100 Ode KS solvent 30

EXAMPLE A3

An image was printed on the second layer of the sample produced inExample A1 by a gravure printing method to form a designed layer. Asample shown in FIG. 4 was obtained by forming a water repellent layeron the designed layer the same as in Example A2.

EXAMPLE A4

A sample shown in FIG. 5 was produced the same as in Example A1 exceptthat three parts by weight of a commercially available germicide wheresilver was carried in zeolite were added to 68.6 parts by weight of thecoating liquid to form a second layer.

EXAMPLE A5

A sample shown in FIG. 6 was produced the same as in Example A1 exceptthat 0.5 parts by weight of a commercially available triazole fungicidewere added to 68.6 parts by weight of the coating liquid to form asecond layer.

EXAMPLE A6

A sample shown in FIG. 7 was produced the same as in Example A2 exceptthat five parts by weight of commercially available photocatalystictitanium oxide powder were added to 130 parts by weight of the coatingliquid to form a water repellent layer.

EXAMPLE A7

A sample shown in FIG. 8 was produced the same as in Example A1 exceptthat five parts by weight of a fluoric water repellent additive wereadded to 68.6 parts by weight of the coating liquid to form a secondlayer.

EXAMPLE A8

A sample shown in FIG. 9 was produced the same as in Example A1 exceptthat one part by weight of phthalocyanine blue as color pigment wasadded to 68.6 parts by weight of the coating liquid to form a secondlayer.

EXAMPLE A9

An image was printed on the second layer of the sample produced inExample A8 by a gravure printing method to form a designed layer. Asample shown in FIG. 10 was obtained by forming a water repellent layeron the designed layer the same as in Example A2.

COMPARATIVE EXAMPLE A1

A sample shown in FIG. 11 where only the first layer was formed wasproduced the same as in Example A1 except that the second layer was notformed.

COMPARATIVE EXAMPLE A2

A sample shown in FIG. 12 was produced by forming the water repellentlayer the same as in Example A2 on the first layer of the sampleobtained in Comparative Example A1.

COMPARATIVE EXAMPLE A3

A sample where only the first layer was formed was produced the same asin Example A1 except that the second layer was not formed. A sampleshown in FIG. 13 where a moisture permeable/water proofing film waslaminated on the first layer was produced. As the moisturepermeable/water proofing film, a polyethylene porous film (Polum PUH 35having 35 μm thickness and 1.1 μm maximum fine pore diameter made byTOKUYAMA Corp.) was used.

COMPARATIVE EXAMPLE A4

A sample where only the first layer was formed was produced the same asin Example A1 except that the second layer was not formed. Waterpolyurethane resin was applied on the first layer by a gravure printingmethod so that the thickness thereof after drying became 5 μm to bedried, thereby producing a sample shown in FIG. 14. As the waterpolyurethane resin, a surface treatment agent for Daiplacoat AQW(product name) made by Dainichiseika Color & Chemicals Mfg. Co., Ltd.)was used.

COMPARATIVE EXAMPLE A5

A commercially available vinyl cloth was used as a sample.

With respect to each sample of Examples A1 to A9 and ComparativeExamples A1 to A5 obtained, tests 1 to 7 were made. The result is asfollows. TABLE 4 Moisture Moisture Water Absorbing Releasing Soluble TarProperties Properties Soy Blue ΔE (g/m²) (g/m²) Coffee Sauce Ink ExampleA1 9.4 100 100 B B B Example A2 8.7 99 99 A A A Example A3 7.6 99 99 A AA Example A4 9.1 98 98 B B B Example A5 8.6 97 97 B B B Example A6 8.898 98 A A A Example A7 9.2 99 99 A A A Example A8 7.9 98 98 B B BExample A9 7.6 96 96 A A A Comparative 22.5 101 101 B B B Example A1Comparative 19.7 98 98 A A A Example A2 Comparative 12.5 61 58 A A BExample A3 Comparative 10.5 76 75 A A B Example A4 Comparative 8.9 8 8 BB C Example A5

Test 1: as shown in Table 4, it is found out that the samples ofExamples A1 to A9 each having the first layer and the second layer haveexcellent antifouling properties to cigarette tar as compared to thesamples of Comparative Examples A1 and A2 without the second layer.

Test 2: as shown in Table 4, it is found out that moistureabsorbing/releasing properties of the samples of Examples A1 to A9 donot deteriorate nearly as compared to the samples of Comparative ExampleA1 without the second layer. And it is found out that moistureabsorbing/releasing rates of the samples of Examples A1 to A9 do notdeteriorate nearly, either as shown in FIG. 2.

In Example A4 and Example A5 in which a germicide and a fungicide werecompounded in the second layer, antifouling properties to tar andmoisture absorbing/releasing properties both were good regardless ofaddition of the germicide and the fungicide. With respect to Example A3where the designed layer was formed between the second layer and thewater repellent layer, Example A8 where color pigment was added to thesecond layer, and Example A9 where the designed layer and the waterrepellent layer were further formed in the sample of Example A8, theantifouling properties to tar and the moisture absorbing/releasingperformance both were good.

In the sample of Comparative Example A3 where the moisturepermeable/water proofing film was laminated and in the sample ofComparative Example A4 using the urethane resin, the antifoulingproperties to tar were exhibited to some degrees, but an effect of theantifouling properties was smaller as compared to the Examples, and themoisture absorbing/releasing performance was deteriorated. The moistureabsorbing/releasing rate was remarkably lowered as clearly shown in FIG.2.

Test 3: As shown in Table 4, with respect to Examples A2 and A6 wherethe water repellent layer was formed on the second layer, Examples A3and A9 where the designed layer and the water repellent layer wereformed on the second layer, and Example A7 where the water repellentadditive was compounded in the second layer, it is found out that theantifouling properties to stain of liquid such as coffee are also good.

Test 4: Table 5 shows the evaluation result of antibacterialperformance. TABLE 5 Antibacteria Active Value Staphylococcus Exampleaureus Coli bacteria Example A4 4.1 6.5 Comparative 0.1 0.2 Example A1Comparative 0.2 0.1 Example A5

As clearly seen from Table 5, with respect to the sample of Example A4where a germicide was compounded, the antibacterial active value thereofwas far beyond 2.0 in the staphylococcus aureus and the coli bacteria,and good antibacterial properties were confirmed. On the other hand, inthe commercially available vinyl clothes of Comparative Example A1 andComparative Example A5 where the germicide was not compounded, theantibacterial properties were not found out.

Test 5: Table 6 shows the evaluation result of antifungal performance.TABLE 6 Example Evaluation Example A5 No growth of fungal threadComparative Example A1 Growth of fungus on the entire surface of oneside of the test piece Comparative Example A5 Growth of fungus on ½ ofthe entire surface of one side of the test piece

As clearly seen from Table 6, with respect to the sample of Example A5where the fungicide was compounded, growth of the fungal threads was notfound out even under the 40 time microscope and good antifungalperformance was confirmed. On the other hand, in the commerciallyavailable vinyl clothes of Comparative Example A1 and ComparativeExample A5 where the fungicide was not compounded, the antifungalperformance was not found out.

Test 6: Evaluation of Flexibility

All of the evaluation results of the samples in Examples A1 to A9 were“A” (no crack).

Test 7: Evaluation of Firesafety

All of the samples of Examples A1 to A9 showed a total heat value of 8MJ/m² or less and “passed.”

EXAMPLE B1

As a base material, a base material paper for wall papers having threelayered structure comprising a backing paper, a film, and a non-wovenfabric was prepared. The weight of the base material paper for wallpapers was 111 g/m². A commercially available triazole fungicide wasprepared as a water soluble fungicide. Activated alumina was prepared asan inorganic porous material. Measurements 1 and 2 were made withrespect to the activated alumina. As a result, the volume of the finepore diameter of 4 to 14 nm was 0.41 ml/g, the total fine pore volumewas 0.50 ml/g, and the average particle diameter was 30 μm. Commerciallyavailable acrylic emulsion was prepared as organic emulsion. Themeasurements 4 and 6 were made with respect to the emulsion. As aresult, the glass-transition temperature was −43° C., and the averageparticle size was 0.25 μm, and the active substance were 60%.

Raw materials were put in the mixer based upon the compound shown inTable 7 and mixed therein to obtain an coating liquid. This coatingliquid was applied on the base material using a comma coater in such amanner that the thickness after drying became 350 μm, and dried thecoating liquid at 150° C. to form a first layer. TABLE 7 Formulation ofHumidity-controlling Layer Coating Composition Formulation Part byweight Activated alumina 70 Acrylic emulsion 30 Triazole fungicide 0.5Dispersing agent 17.5 [Flowlen TG - 750 W made by Kyoeisya Chemical Co.,Ltd.] Wetting agent 0.5 [Flowlen D - 90 made by Kyoeisya Chemical Co.,Ltd.] Defoamer 0.5 [Aqualen 8020 made by Kyoeisya Chemical Co., Ltd.]Water 40

The coating liquid was prepared based upon the compound in Table 8. Thiscoating liquid was applied on the first layer by screen printing to forma second layer thereon. TABLE 8 Compound Part by Weight Titanium oxide10 Calcium carbonate 20 Organic emulsion 20 Dispersing agent 3 Wettingagent 0.4 Antifoamer 0.2 Water 10

Next, The foam print paint was prepared based upon the formulation inTable 9. After the paint was coated by screen printing, the paint washeated at 150° C. to foam the paint, thereby producing a functional wallpaper where the designed layer was further formed on the second layer.TABLE 9 Formulation of Foam Printing Paint Formulation Part by WeightEthylene-polyvinyl acetate copolymer emulsion 100 [Panflex OM 4200 madeby KURARAY CO., LTD.] Foaming agent 6 [AZ# 3051 made by Otsuka ChemicalCo., Ltd.] Calcium carbonate 20 Titanium oxide for pigment 15 Water 20

With respect to the sample of Example B1 obtained, Tests 1, 2, 5, and 6were made. The result is as follows.

Test 1: The result for cigarette stain test showed that the colordifference ΔE* was 8.4.

Test 2: Moisture absorbing properties were 101 g/m² and moisturereleasing properties were 100 g/m².

Test 5: Evaluation of antifungal properties was [5].

Test 6: Evaluation of flexibility was “A” (no crack).

COMPARATIVE EXAMPLE B1

A first layer was formed the same as in Example B1 except that insteadof the water soluble fungicide of Example B1, a commercially availablewater insoluble fungicide where copper was fixed to titanium oxide wasused and formation of the second layer was not made.

With respect to the sample of the Comparative Example B 1, Tests 1, 2,5, and 6 were made.

The result is as follows.

Test 1: The result for cigarette stain test showed that the colordifference ΔE* was 15.8.

Test 2: Moisture absorbing properties were 100 g/m² and moisturereleasing properties were 99 g/m².

Test 5: Evaluation of antifungal properties was “1”.

Test 6: Evaluation of flexibility was “A” (no crack).

EXAMPLE C1

As a flexible base material, a base material paper for wall papershaving three layered structure comprising a backing paper, a film, and anon-woven fabric was prepared. Commercially available activated aluminawas prepared as an inorganic porous material. Measurements 1 to 3 weremade with respect to the activated alumina. As a result, the volume ofthe fine pore having a diameter of 4 to 14 nm was 0.46 ml/g, the totalfine pore volume was 0.50 ml/g, the bulkiness density was 680 g/L, andthe average particle size was 30 μm. Commercially available acrylicemulsion was prepared as organic emulsion. Measurements 4 and 6 weremade with respect to the emulsion. As a result, the glass-transitiontemperature was −43 ° C., the active substance was 60%, the bulkinessdensity of the dry matter was 1200 g/L, and the average particle sizewas 0.2 μm. Raw materials were put in the mixer based upon theformulation shown in Table 10 and mixed therein to obtain an coatingliquid. This coating liquid was applied on the base material using acomma coater in such a manner that the thickness after drying became 300μm, to form a first layer. TABLE 10 Part by Weight Formulation (Part byVolume) Activated alumina 75 (441) Acrylic emulsion(active substance) 30(100) Dispersing agent 17.5 Wetting agent 0.5 Antifoamer 0.5 Water 40

Titanium oxide and calcium carbonate were prepared as an inorganicparticulate. When the measurement 2 was made with respect to theinorganic particulate, an average particle diameter of the titaniumoxide was 5 μm and an average particle diameter of the calcium carbonatewas 3 μm. Organic emulsion (ethylene vinyl acetate) was prepared as anorganic binder. When the measurement 6 was made with respect to theorganic emulsion, the glass-transition temperature was 0° C. Next, thecoating liquid was prepared based upon the formulation in Table 11. Thecoating liquid was applied on the first layer by screen printing so thatthe thickness of the second layer after drying was 10 μm. Next, thecoating liquid was dried at 150° C. to obtain a functional member wherethe second layer was formed on the first layer. TABLE 11 FormulationPart by Weight Titanium oxide 10 Calcium carbonate 20 Organic emulsion20 Dispersing agent 3 Wetting agent 0.4 Antifoamer 0.2 Water 10

EXAMPLE C2

The functional member where the second layer was formed on the firstlayer was produced the same as in Example C1. Next, a foam print paintwas prepared based upon the formulation in Table 12. After the paint wasapplied by screen printing, the paint was heated at 150° C. to foam thepaint, thereby producing a functional member where a designed layer wasfurther formed on the second layer. TABLE 12 Formulation Part by WeightEthylene-polyvinyl acetate copolymer emulsion 100 [Panflex OM 4200 madeby KURARAY CO., LTD.] Foaming agent 6 [AZ# 3051 made by Otsuka ChemicalCo., Ltd.] Calcium carbonate 20 Titanium oxide for pigment 15 Water 20

EXAMPLE C3

The functional member where the second layer and the designed layer wereformed on the first layer was produced the same as in Example C2. Next,a water repellent treatment agent was prepared based upon theformulation in Table 13. After the water repellent treatment agent wasapplied by gravure printing, thereby producing a functional member wherea water repellent treatment layer was further formed on the designedlayer. TABLE 13 Formulation Part by Weight Water repellent treatmentagent 9 [Asahi guard AG - 533 made by Asahi Glass Corp.] Viscosityincreasing agent 0.5 Water 200

With respect to the samples of Examples C1 to C3 obtained, Tests 1 to 3,6, 8, and 9 were made. The result is as follows. TABLE 14 MoistureMoisture Contamination Contacting Absorbing Releasing CigaretteResistant Angle Appearance Flexibility Properties Properties StainProperties (degree) Example C1 A A 109 108 8.1 A 84 Example C2 A A 103101 6.7 A 92 Example C3 A A 102 101 6.4 A 121 

1. A functional member, comprising: a flexible base material, a firstlayer which is formed on the base material and comprises a dry matter ofa mixture comprising an inorganic porous material and an organicemulsion, and a second layer comprising an inorganic filler which isfixed over an approximately entire surface of the first layer by anorganic binder, wherein the organic matter in the organic emulsion has aglass-transition temperature of −5° C. to −50° C.; wherein the firstlayer comprises 200 to 500 parts by weight of the inorganic porousmaterial to 100 parts by weight of a dry matter in the organic emulsion;and wherein the organic binder in the second layer is contained in anamount of 30-300 parts by volume to 100 parts by volume of the inorganicfiller.
 2. The functional member according to claim 1, wherein thesecond layer has a coat thickness of 1 to 100 μm.
 3. The functionalmember according to claim 1, wherein the inorganic filler has a particlesize of equal to or less than 60 μm.
 4. The functional member accordingto claim 1, wherein the inorganic filler comprises at least one of thetitanium oxide and calcium carbonate.
 5. The functional member accordingto claim 1, wherein the organic binder is a cured matter of the organicemulsion.
 6. The functional member according to claim 5, wherein theglass-transition temperature of the organic matter in the organicemulsion for the second layer is −10° C. to 30° C.
 7. The functionalmember according to claim 1, further comprising a designed layer formedon a surface of the second layer.
 8. The functional member according toclaim 1, further comprising a water repellent layer formed on a surfaceof the second layer.
 9. The functional member according to claim 1,wherein the second layer further comprises at least one of a germicideand a fungicide.
 10. The functional member according to claim 8, whereinthe water repellent layer further comprises at least one of a germicideand a fungicide.
 11. The functional member according to claim 1, whereinthe second layer further comprises a photocatalyst.
 12. The functionalmember according to 8, wherein the water repellent layer furthercomprises a photocatalyst.
 13. The functional member according to claim1, wherein the second layer further comprises a water repellentadditive.
 14. The functional member according to claim 1, having avolume of a fine pore of which a diameter is 4-14 nm measured bynitrogen gas adsorption of the inorganic porous material being equal toor more than 0.1 ml/g; and a total volume of all the fine pores of whicheach diameter is 1-200 nm measured by nitrogen gas adsorption of theinorganic porous material being equal to or less than 1.5 ml/g. 15.(canceled)
 16. The functional member according to claim 5, wherein theorganic emulsion for the first layer has a dry weight of equal to orless than 100 g/m²; the organic emulsion for the second layer has a dryweight of equal to or less than 50 g/m²; and the functional member has aweight of all organic matters including the base material of equal to orless than 300 g/m².
 17. The functional member according to claim 1,wherein the first layer further comprises a water soluble fungicide. 18.The functional member according claim 1, wherein the first layercomprises 400 to 1200 parts by volume of the inorganic porous materialto 100 parts by volume of the dry matter in the organic emulsion. 19.The functional member according to claim 1, having a volume of a finepore of which a diameter is 4-14 nm measured by nitrogen gas adsorptionof the inorganic porous material being equal to or more than 0.2 ml/g;and a total volume of all the fine pores of which each diameter is 1-200nm measured by nitrogen gas adsorption of the inorganic porous materialbeing equal to or less than 1.3 ml/g.
 20. The functional memberaccording to claim 1 wherein the first layer further comprises anon-porous filler.
 21. The functional member according to claim 20,wherein the first layer comprises 400 to 1100 parts by volume of theinorganic porous material and 50 to 500 parts by volume of thenon-porous filler to 100 parts by volume of the dry matter in theorganic emulsion; and a total amount of the inorganic porous materialand the non-porous filler is 400 to 1200 parts by volume.
 22. Thefunctional member according to claim 20, having a volume of a fine poreof which a diameter is 4-14 nm measured by nitrogen gas adsorption ofthe inorganic porous material being equal to or more than 0.4 ml/g; anda total volume of all the fine pores of which each diameter is 1-200 nmmeasured by nitrogen gas adsorption of the inorganic porous materialbeing equal to or less than 1.6 ml/g.
 23. The functional memberaccording claim 1, further comprising a designed layer formed on asurface of the second layer and a coating layer of a dry matter of aresin colloidal dispersion is formed on a surface of the designed layer.24. (canceled)
 25. The functional member according to claim 1, whereinthe base material is selected from the group consisting of a paper, asynthetic resin sheet, a woven fabric, a non-woven fabric, a glass fibersheet, a metal fiber, a flame-retardant backing paper, a base materialpaper for wall papers, a composite and a laminated material thereof. 26.An A coating liquid for forming the first layer of the functional memberaccording to claim 1, comprising an inorganic porous material and anorganic emulsion, wherein the organic matter in the organic emulsion hasa glass-transition temperature of −5° C. to −50° C., and wherein 200 to500 parts by weight of the inorganic porous material is contained to 100parts by weight of a dry matter in the organic emulsion.
 27. The coatingliquid according to claim 26, further comprising a non-porous filler.28. A method of manufacturing a functional member according to claim 1,comprising the steps of: providing a flexible base material, applying acoating liquid on the base material, drying the coating liquid to form afirst layer, and applying a mixture of an inorganic filler and anorganic binder over an approximately entire surface of the first layerto form a second layer, wherein the organic binder in the second layeris contained in an amount of 30-300 parts by volume to 100 parts byvolume of the inorganic filler, and wherein the coating liquid comprisesan inorganic porous material and an organic emulsion, wherein theorganic matter in the organic emulsion has a glass-transitiontemperature of −5° C. to −50° C., and wherein 200 to 500 parts by weightof the inorganic porous material is contained to 100 parts by weight ofa dry matter in the organic emulsion.
 29. The functional memberaccording to claim 7, further comprising a water repellent layer formedon a surface of the designed layer.
 30. The functional member accordingto claim 7, wherein the designed layer further comprises aphotocatalyst.